Linking the Rb and Polycomb PathwaysIn this article (Mol. Cell 8, 557-568, September 2001), errors are present in three of the figures. We apologize for these errors; however, we continue to support the conclusions reached in the original manuscript. The corrected figures along with their legends are reproduced on the following pages.

The upsurge interesti nt he development of efficient methodologies for the constructiono fn itrogen-containing frameworks via the use of expedient reagents have been creating ar enaissance in contemporary organic chemistry.I nt his perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its uniques tructuralf eatures, it shows differential reactivity under different reaction conditions. These diverse reactivities have resulted in the construction of ad iverse array of complex N-containing molecules. The primary objective of the presentr eview is to bring the latest findings of TBN in terms of its applications in reactions (oxidation, diazotization, nitrosation, nitration, oximation, N-synthon, and miscellaneous reactions) into the limelight.F or simplicity and brevity,r eactions in each section are explained with the mechanism of formation and selected examples are given.Scheme1.Differential reactivity of TBN. 4455 MinireviewScheme4.Visible-light-promoted synthesis of selenide ethers.Scheme5.Proposed mechanism for visible-light-promoted synthesis of selenide ethers.Scheme6.TBN-mediated synthesis of selenide ethers.Scheme7.Metal-free synthesis of 4-carbonylquinolines.Scheme8.Proposed mechanism for synthesis of 4-carbonylquinolines.Scheme9.TBN-mediated demethylative borylation of methylarenes.Scheme10. Plausible mechanism for demethylative borylation of methylarenes.Scheme11. Trifluoromethylation of various aromatic amine substrates.Scheme12. Copper-catalyzed isoperfluoropropylation of anilines.Scheme13. Plausible mechanism for Cu-catalyzed isoperfluoropropylation of anilines.Scheme14. TBN-mediateddiazotizative allylation of aromatic amines.Scheme15. Oxidativecyanomethylationo fa lkenes via CÀHb ond activation.Scheme16. TBN-mediatedand Cu-catalyzedsynthesis of thioether.

An inimitable illustration of the green-light-induced synthesis of thio-functionalized pyrroles has been established using β-ketodinitriles and thiophenols as the reacting partners and eosin Y as the photocatalyst. Large-scale synthesis and some useful synthetic modifications of the thio-functionalized pyrroles are also demonstrated.

A visible-light-induced synthesis of N-hydroxybenzimidoyl cyanides from aromatic terminal alkenes is achieved by using Eosin Y as an organic photoredox catalyst. The process goes via a radical pathway with successive incorporation of two nitrogen atoms, one each from tert-butyl nitrite and ammonium acetate. The final product is achieved by the concomitant installation of an oxime and a nitrile group. DFT calculation supports a biradical pathway and all the proposed steps. A few useful synthetic transformations of N-hydroxybenzimidoyl cyanide are also illustrated.

A catalyst-free regioselective synthesis of 2-iminothiazolidines has been achieved by reacting unactivated aziridines with aroyl isothiocyanates at ambient temperature in 100% atom economy via a domino ring opening cyclization. The present protocol operates under solvent free conditions as well as in the absence of any catalyst making it a greener and ecofriendly approach.

An inimitable illustration of a green-light-induced, regioselective difunctionalization of terminal alkynes has been disclosed using sodium arylsulfinates and carboxylic acids in the presence of eosin Y as the photocatalyst. The present methodology is further demonstrated by employing NH 4 SCN as an S-centered nucleophile instead of carboxylic acid. The mechanistic investigation reveals a radical-induced iodosulfonylation followed by a base-mediated nucleophilic substitution. The mechanism is supported by various studies, viz., radical-trapping experiment, fluorescence quenching, and CV studies. In this protocol, (Z)-βsubstituted vinylsulfones are obtained, exclusively covering a broad range of alkynes and nucleophiles, which are often unaddressed. The present strategy can tolerate structurally discrete substrates with steric bulk and different electronic properties, which provides a straightforward and practical pathway for the synthesis of highly functionalized (Z)-β-substituted vinylsulfones. Herein, C−O and C−S bonds are assembled simultaneously with the concomitant introduction of important functional groups, viz., ester, thiocyanate, and sulfone.

The in situ generated o-alkynylthioureas obtain by reacting 2-(phenylethynyl)anilines and aryl isothiocynates undergo efficient cascade cyclization in the presence of AgCO to form indoloquinolines under microwave heating. The present tandem process allows the generation of a variety of indolo[2,3-b]quinolines derivatives in good to moderate yields with a wide functional group tolerance.

Hypervalent iodine (HVI) chemistry is a rapidly growing subdomain of contemporary organic chemistry because of its enormous synthetic applications. The high nucleofugality of the phenyliodonio group (I+Ph) and their radical...